Preparation of cyanomethyl dialkyl orthoformates



UNITED STATES PATENT OFFICE PREPARATION OF CYANOMETHYL DIALKYL ORTHOFORM'ATES Donald J. Loder and William F. Gresham, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application September '7, 1944, Serial No. 553,108

Claims. (Cl. 2 60464) 2 V This invention relates to the preparation of charged with 28.5 parts (0.5 M) of formaldehyde orthoformates and more particularly cyanoalkyl a pressure of approximately 105 mm. During the dialkyl orthoformates by reacting alkyl orthofordistillation 31.6 parts of ethanol is recovered. The mates with aldehyde cyanhydrins. Yet another product is then fractionated under a reduced are realized bysu'bjecting an alkyl orthoiormate This exairiple illustrates the advantages dethe process at a temperature ranging between 75 Example II.-The process of Example I is subrated and purlfied by fr c l n I and the cyanomethyl diethyl orthoformate obhe reaction is illustrated by the generic tained in a yield of approximately 56.2%.

equation: The process illustrated in the examples may be HCXOR) 3+HORICN HC(OR) 2OR1CN+ROHV used for the preparation of a number of related in which R designates an alkyl and B1 an alkylene produced by reacting the aldehyde cyanhydrins presence of an eizcess of the alkyl orthoformate 4r) athyl, methylpropyl, thylethylpropyl, and simiexamples in which parts are by weight unless otherwise indicated. general equatwn' Ervample I.A round bottom glass flask is HC(OR)zOR1CN+H2eHC(0R)on wherein R is an alkyl group and R1 an alkylene pressure, is obtained upon fractionation of the group. More specifically, valuable amines such product.

as aminoethyl diethyl orthoformate may be ob- Example IV.The process of Example III is tained in accord with the equation: substalrsltially duplicated. employing 40 parts m (0.25 of cyanomethyl diethyl orthoformate, HC(OC2H5)2OCH2CN+2H2' 85 parts (5 M) of anhydrous ammonia and,

- HC(OC2H5) zOCHzCHzNHz parts of a nickel catalyst supported on kieselguhr.

The hydrogenation of the aminoethyl ortho- This reaction is conducted at a temperature beformates is preferably conducted under superattween 103 and 125 C. for approximately 4 hours mospheric pressur between 50 n 1 m s under a hydrogen pressure of about 700 at- P s and at temperatures ranging t een 0 mospheres. Approximately an 87.5% conversion and. 150 C. Any s table hydr n ti n aly s of the nitrile to the amine is realized.

may be employed such, for example, as nickel W l supported on kieselguhr, Raney nickel catalysts, 1, A process for the preparation of a. cyanocobalt catalysts, nickel chromite catalysts and the i5 methyl dial 1 orthoformate which comprises like. subjecting formaldehyde cyanhydrin to a reac- The examples which follow illustrate p tion with an alkyl orthoformate in the presence of methods of converting the cyanoalkyl orthoiora condensation catalyst,

mates to aminoalkyl orthoformates. In these 2. A process for the preparation of a cyanoexamples parts are by weight unless otherwise methyl diethyl orthoformate which comprises indicated. subjecting formaldehyde cyanhydrin to a reac- Exdmple II I .-*A silver-lined pressure-resisting tion with ethyl orthoiormate in the presence of autoclave is charged with 31.8 parts (0.2 M) of a condensation catalyst.

cyanomethyl diethyl orthoformate, 85 parts (5 M) 3. A process for the preparation of a cyanoof anhydrous ammonia and 20 parts of a nickel methyl dialkyl orthoformate which comprises catalyst supported on kieselguhr. The reaction is subjecting an aldehyde cyanhydrin to a reaction conducted at a temperature between 108 and with a molar excess of an alkyl orthoformate at 112 C. under a hydrogen pressure of about 700 a temperature between and C. and in the atmospheres and for approximately 1 /2 hours. presence of zinc chloride as the catalyst. Pressure is then released from the autoclave after 30 4. A cyanomethyl dialkyl orthoiormate. lowering the temperature and a 75.6% yield of 5. Cyanomethyl diethyl orthoformate. beta-amihoethyl diethyl orthoformate, a colorless DONALD J. LODER.

liquid having a boiling point of 88 C. at 10 mm. WILL AM F. GRESHAM. 

